JP2004107654A - Cationic electrodeposition coating composition for galvanized steel sheet - Google Patents
Cationic electrodeposition coating composition for galvanized steel sheet Download PDFInfo
- Publication number
- JP2004107654A JP2004107654A JP2003299021A JP2003299021A JP2004107654A JP 2004107654 A JP2004107654 A JP 2004107654A JP 2003299021 A JP2003299021 A JP 2003299021A JP 2003299021 A JP2003299021 A JP 2003299021A JP 2004107654 A JP2004107654 A JP 2004107654A
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- JP
- Japan
- Prior art keywords
- compound
- mass
- electrodeposition coating
- coating composition
- silicate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 238000004070 electrodeposition Methods 0.000 title claims abstract description 67
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 58
- 239000008199 coating composition Substances 0.000 title claims abstract description 38
- 229910001335 Galvanized steel Inorganic materials 0.000 title claims description 23
- 239000008397 galvanized steel Substances 0.000 title claims description 23
- -1 silicate compound Chemical class 0.000 claims abstract description 128
- 239000000049 pigment Substances 0.000 claims abstract description 63
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 50
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 37
- 239000003822 epoxy resin Substances 0.000 claims abstract description 36
- 150000002681 magnesium compounds Chemical class 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 23
- 239000010959 steel Substances 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 19
- 150000002500 ions Chemical class 0.000 claims abstract description 9
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 235000012239 silicon dioxide Nutrition 0.000 claims description 12
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 238000007747 plating Methods 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 26
- 230000007797 corrosion Effects 0.000 abstract description 26
- 239000000203 mixture Substances 0.000 abstract description 22
- 239000000243 solution Substances 0.000 abstract description 7
- 239000012670 alkaline solution Substances 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 21
- 239000003973 paint Substances 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 19
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 17
- 239000005056 polyisocyanate Substances 0.000 description 17
- 229920001228 polyisocyanate Polymers 0.000 description 17
- 239000006185 dispersion Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- 238000002474 experimental method Methods 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 14
- 239000004593 Epoxy Substances 0.000 description 13
- 238000001723 curing Methods 0.000 description 13
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000009472 formulation Methods 0.000 description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000004580 weight loss Effects 0.000 description 9
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 238000010828 elution Methods 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 238000007654 immersion Methods 0.000 description 7
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000002966 varnish Substances 0.000 description 7
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000012736 aqueous medium Substances 0.000 description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- WDGCBNTXZHJTHJ-UHFFFAOYSA-N 2h-1,3-oxazol-2-id-4-one Chemical group O=C1CO[C-]=N1 WDGCBNTXZHJTHJ-UHFFFAOYSA-N 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000005995 Aluminium silicate Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000002981 blocking agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 3
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000010960 cold rolled steel Substances 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 150000002611 lead compounds Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 150000003335 secondary amines Chemical class 0.000 description 3
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 2
- XEFUJGURFLOFAN-UHFFFAOYSA-N 1,3-dichloro-5-isocyanatobenzene Chemical compound ClC1=CC(Cl)=CC(N=C=O)=C1 XEFUJGURFLOFAN-UHFFFAOYSA-N 0.000 description 2
- OHJYHAOODFPJOD-UHFFFAOYSA-N 2-(2-ethylhexoxy)ethanol Chemical compound CCCCC(CC)COCCO OHJYHAOODFPJOD-UHFFFAOYSA-N 0.000 description 2
- FOLVZNOYNJFEBK-UHFFFAOYSA-N 3,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane Chemical compound C1C(CN=C=O)C2C(CN=C=O)CC1C2 FOLVZNOYNJFEBK-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CETBSQOFQKLHHZ-UHFFFAOYSA-N Diethyl disulfide Chemical compound CCSSCC CETBSQOFQKLHHZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QCOGKXLOEWLIDC-UHFFFAOYSA-N N-methylbutylamine Chemical compound CCCCNC QCOGKXLOEWLIDC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 125000001302 tertiary amino group Chemical group 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- AFPIWWDEGJLLCL-UHFFFAOYSA-N 1,3,2,4$l^{2}-dioxasilaplumbetane 2-oxide Chemical compound [Pb+2].[O-][Si]([O-])=O AFPIWWDEGJLLCL-UHFFFAOYSA-N 0.000 description 1
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical compound O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- WNNRUOPGOIGERJ-UHFFFAOYSA-N 1-(2-hydroxyethylsulfanyl)propan-2-ol Chemical compound CC(O)CSCCO WNNRUOPGOIGERJ-UHFFFAOYSA-N 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
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- VNGLVZLEUDIDQH-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;2-methyloxirane Chemical compound CC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 VNGLVZLEUDIDQH-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
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- 239000004606 Fillers/Extenders Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- HDONYZHVZVCMLR-UHFFFAOYSA-N N=C=O.N=C=O.CC1CCCCC1 Chemical compound N=C=O.N=C=O.CC1CCCCC1 HDONYZHVZVCMLR-UHFFFAOYSA-N 0.000 description 1
- JTDWCIXOEPQECG-UHFFFAOYSA-N N=C=O.N=C=O.CCCCCC(C)(C)C Chemical compound N=C=O.N=C=O.CCCCCC(C)(C)C JTDWCIXOEPQECG-UHFFFAOYSA-N 0.000 description 1
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910002051 SYLYSIA SY530 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000004110 Zinc silicate Substances 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- FZENGILVLUJGJX-UHFFFAOYSA-N acetaldehyde oxime Chemical compound CC=NO FZENGILVLUJGJX-UHFFFAOYSA-N 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- MNFORVFSTILPAW-UHFFFAOYSA-N azetidin-2-one Chemical compound O=C1CCN1 MNFORVFSTILPAW-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- XMYLSWOTJKUSHE-UHFFFAOYSA-N cyanamide;lead Chemical compound [Pb].NC#N XMYLSWOTJKUSHE-UHFFFAOYSA-N 0.000 description 1
- FSEUPUDHEBLWJY-HWKANZROSA-N diacetylmonoxime Chemical compound CC(=O)C(\C)=N\O FSEUPUDHEBLWJY-HWKANZROSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- ZOIVSVWBENBHNT-UHFFFAOYSA-N dizinc;silicate Chemical compound [Zn+2].[Zn+2].[O-][Si]([O-])([O-])[O-] ZOIVSVWBENBHNT-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical class CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical compound ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- AUTOISGCBLBLBA-UHFFFAOYSA-N trizinc;diphosphite Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])[O-].[O-]P([O-])[O-] AUTOISGCBLBLBA-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000019352 zinc silicate Nutrition 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、亜鉛めっき鋼板用カチオン電着塗料組成物に関し、特に無鉛性の亜鉛めっき鋼板用カチオン電着塗料組成物に関する。 The present invention relates to a cationic electrodeposition coating composition for galvanized steel sheets, and particularly to a lead-free cationic electrodeposition coating composition for galvanized steel sheets.
工業材料として使用される亜鉛鋼板の種類には、一般に電気亜鉛めっき鋼板、溶融亜鉛めっき鋼板、及び亜鉛−ニッケル鋼板等がある。この中で、例えば、電気亜鉛めっき鋼板は、めっきされた亜鉛の純度が高く活性であり、亜鉛−ニッケル鋼板等よりも特にアルカリ性条件下での耐食性に劣るという問題がある。 亜 鉛 In general, galvanized steel sheets, hot-dip galvanized steel sheets, zinc-nickel steel sheets and the like are used as industrial materials. Among them, for example, an electrogalvanized steel sheet has a problem that the purity of the plated zinc is high and active, and it is inferior to a zinc-nickel steel sheet or the like in corrosion resistance particularly under alkaline conditions.
そのため、屋外で風雨に晒され、高い耐食性が要求される、例えば、自動車車体等の用途には、これまで亜鉛−ニッケル鋼板が主として使用されてきた。しかし、近年の経済情勢から原料コストの低減が重要な課題となりつつあり、そのため、亜鉛−ニッケルめっき鋼板よりもコスト的に安価な電気亜鉛めっき鋼板の使用が検討されるようになってきた。従って、このようなアルカリ条件下でも耐食性を向上させることができる電気亜鉛めっき鋼板の処理方法が求められていた。 亜 鉛 Therefore, zinc-nickel steel sheets have been mainly used for applications such as automobile bodies that are exposed to wind and rain outdoors and have high corrosion resistance. However, reduction of raw material costs has become an important issue due to recent economic conditions, and therefore, use of electrogalvanized steel sheets which are cheaper in cost than zinc-nickel plated steel sheets has been studied. Therefore, there has been a demand for a method for treating an electrogalvanized steel sheet that can improve corrosion resistance even under such alkaline conditions.
電着塗装は導電性基材の上に塗装する技術であり、その非常に重要な性能は防錆性である。塗装された基材は、多種多様な腐食環境にさらされるが、どのような環境下においても高い防錆性が要求される。 Electrodeposition coating is a technique of coating on a conductive substrate, and its very important performance is rust prevention. Painted substrates are exposed to a wide variety of corrosive environments, and high rust resistance is required under any environment.
一方、これまで電着塗料には、耐食性を付与するため、鉛を含む耐食性付与剤が添加されてきた。近年、鉛は環境に対して悪影響を与えることから、使用量の削減が要求されており、そうした鉛を含む耐食性付与剤を含まない、いわゆる無鉛性カチオン電着塗料が主として利用されつつある。しかし、鉛を使用しないことにより耐食性が低下することが多く、特に電気亜鉛めっき鋼板を無鉛性電着塗料組成物で電着塗装した基材は、耐食性が劣ることとなる。 On the other hand, a corrosion resistance imparting agent containing lead has been added to electrodeposition paints in order to impart corrosion resistance. In recent years, since lead has a bad influence on the environment, it has been required to reduce the amount of use, and so-called lead-free cationic electrodeposition coatings which do not contain such a lead-containing corrosion-resistance imparting agent have been mainly used. However, when lead is not used, the corrosion resistance often deteriorates. In particular, a substrate obtained by electrodepositing an electrogalvanized steel sheet with a lead-free electrodeposition coating composition has poor corrosion resistance.
本発明の目的は、従来あまり検討の対象になっていない基材、即ち亜鉛めっき鋼板に対して高い防錆性能を発揮する実質上鉛化合物もしくは鉛イオンを含まない電着塗料を提供することにある。 An object of the present invention is to provide an electrodeposition paint substantially free of lead compounds or lead ions, which exhibits high rust-preventive performance on a base material which has not been studied so far, that is, a galvanized steel sheet. is there.
即ち、本発明は、ケイ酸化合物を１質量％含有するｐＨ１２のアルカリ性水溶液中に溶出したケイ酸イオンの平衡濃度が５０ppm〜３０００ppmであるケイ酸化合物を含有する、亜鉛めっき鋼板用カチオン電着塗料組成物を提供するものであり、そのことにより上記課題を解決することができる。
That is, the present invention provides a cationic electrodeposition coating composition for galvanized steel sheets containing a silicate compound having an equilibrium concentration of silicate ions eluted in a
上記カチオン電着塗料組成物は、さらにアルミニウム化合物を含んでもよく、このアルミニウム化合物はアルミニウム化合物１質量％含有ｐＨ１２のアルカリ性水溶液中に溶出したアルミニウムイオンの平衡濃度５０ppm〜３０００ppmを有するものである。 The above cationic electrodeposition coating composition may further contain an aluminum compound, which has an equilibrium concentration of aluminum ions of 50 ppm to 3000 ppm eluted in an alkaline aqueous solution containing 1% by mass of the aluminum compound and having a pH of 12.
上記カチオン電着塗料組成物は、さらにマグネシウム化合物を含んでもよく、このマグネシウム化合物はマグネシウム化合物１質量％含有ｐＨ１２のアルカリ性水溶液中に溶出したマグネシウムイオンの平衡濃度５０ppm〜３０００ppmを有するものである。 The cationic electrodeposition coating composition may further contain a magnesium compound, and the magnesium compound has an equilibrium concentration of 50 ppm to 3000 ppm of magnesium ions eluted in an alkaline aqueous solution containing 1% by mass of the magnesium compound and having a pH of 12.
さらに、カチオン電着塗料組成物において、これらのケイ酸化合物、アルミニウム化合物およびマグネシウム化合物を含有していてもよい。 Furthermore, the cationic electrodeposition coating composition may contain these silicate compounds, aluminum compounds and magnesium compounds.
ここで平衡濃度とは、前記化合物からイオンが溶出してその濃度が平衡に達したときの濃度をいうが、具体的には各化合物１ｇをｐＨ１２のアルカリ水溶液１００ｇ中に添加した場合の、５０℃、３日間後における溶出濃度をいう。また、単に「亜鉛めっき鋼板」との記載は、電気亜鉛めっき、溶融亜鉛めっき、またはこれらに有機コートを施した電気亜鉛めっき鋼板を意味するものとする。 Here, the equilibrium concentration refers to the concentration when ions elute from the compound and the concentration reaches equilibrium. Specifically, when 1 g of each compound is added to 100 g of an aqueous alkaline solution having a pH of 12, 50 g is obtained. C. means the elution concentration after 3 days. Further, the term “galvanized steel sheet” simply means an electrogalvanized steel sheet, a hot-dip galvanized steel sheet, or an electrogalvanized steel sheet obtained by applying an organic coating thereto.
本明細書では、「カチオン電着塗料組成物」との記載は無鉛性カチオン電着塗料組成物を意味する。ここで「無鉛性」とは、実質上鉛化合物もしくは鉛イオンを含まないことをいい、環境に悪影響を与えるような量で鉛を含まないことを意味する。具体的には、カチオン電着浴中の鉛化合物濃度が１００ｐｐｍ、好ましくは５０ｐｐｍを超える量で含まないことをいう。 で は In this specification, the description “cationic electrodeposition coating composition” means a lead-free cationic electrodeposition coating composition. Here, “lead-free” means that it does not substantially contain lead compounds or lead ions, and means that it does not contain lead in an amount that adversely affects the environment. Specifically, it means that the concentration of the lead compound in the cation electrodeposition bath is not included in an amount exceeding 100 ppm, preferably 50 ppm.
カチオン電着塗料組成物にケイ酸化合物等を含有させることにより、亜鉛めっき鋼板の被塗物に電着塗装すると高い耐食性が得られるカチオン電着塗料組成物が得られる。 さ せ る By adding a silicate compound or the like to the cationic electrodeposition coating composition, a cationic electrodeposition coating composition having high corrosion resistance can be obtained by electrodeposition coating on an object to be galvanized steel sheet.
本発明が成立するまで種々の実験と考察が必要であるが、発明の理解に役立つので、ここで説明する。 種 々 Various experiments and considerations are necessary until the present invention is established, but they will be useful for understanding the present invention.
本発明者等は、まず自動車などの基材に使用されている鋼板を三種類選択して、その腐食環境におけるｐＨの影響について実験を行った。その実験は実験１として後述する。選択した鋼板は自動車の基材として現在最も多く利用されている亜鉛−ニッケルめっき鋼板と冷間圧延鋼板(ＳＰＣ)、そしてあまり利用されていない亜鉛めっき鋼板である。結果を示す図１を見れば明らかであるが、ｐＨが５〜１０ぐらいのマイルドな環境下では、各鋼板にあまり腐食における差が生じていないが、ｐＨ１０を越えるとその差が非常に大きくなっていることが解った。 (4) The present inventors first selected three types of steel plates used for base materials of automobiles and the like, and conducted an experiment on the influence of pH in the corrosive environment. The experiment will be described later as Experiment 1. The steel sheets selected are zinc-nickel-coated steel sheets, cold-rolled steel sheets (SPC), which are currently most frequently used as base materials for automobiles, and galvanized steel sheets, which are rarely used. As is clear from FIG. 1 showing the results, there is little difference in corrosion between the steel sheets under a mild environment with a pH of about 5 to 10, but when the pH exceeds 10, the difference becomes very large. I understood that.
そこで、亜鉛めっき鋼板に着目した場合、ｐＨが１０を超えるアルカリ域で防錆性が極端に悪くなるので、アルカリ域における防錆性が高い防錆剤、顔料もしくはイオン種を検討するためにケイ酸イオン、モリブデン酸イオン、リン酸イオン、マグネシウムイオン、アルミニウムイオンおよび亜鉛イオンについてｐＨ１１における腐食減量を測定した。その実験は後述の実験２に記載されている。その結果は図２を見れば明らかであるが、ケイ酸イオンの腐食抑制効果が極めて高いことが解る。
Therefore, when attention is paid to galvanized steel sheets, the rust resistance is extremely poor in an alkaline region where the pH exceeds 10, and therefore, in order to examine a rust inhibitor, a pigment, or an ionic species having a high rust resistance in an alkaline region, it is necessary to use a silicate. Corrosion weight loss at pH 11 was measured for acid ions, molybdate ions, phosphate ions, magnesium ions, aluminum ions and zinc ions. The experiment is described in
前述のように、ケイ酸イオンが高い防錆性能をｐＨが高いアルカリ域で発揮することが解ったので、そのケイ酸イオン濃度はどれぐらい必要なのかについて検討した。その実験は実験３として後述する。この実験結果は図３、図４に記載している。この結果から明らかなように、ｐＨ１２でも、また１２.６でもケイ酸イオン濃度が約５０ｐｐｍを超える範囲で高い防錆性能を発揮することがわかる。この実験３では、ケイ酸イオンのほかにアルミニウムイオンの存在による効果の促進作用も同時に見ているが、ケイ酸イオンとアルミニウムイオンが同時にあるときに高い防錆作用を示すことも確認できる。
(4) As described above, it was found that silicate ions exerted high rust-preventive performance in an alkaline region having a high pH, and therefore, the required silicate ion concentration was examined. The experiment will be described later as Experiment 3. The results of this experiment are shown in FIGS. As is evident from the results, it can be seen that even at
本発明では、上記考察に基づいて、亜鉛めっき鋼板に好適な高い防錆性を示すカチオン電着塗料に到達した。以下その塗料を詳細に説明する。 で は In the present invention, based on the above consideration, a cationic electrodeposition paint having high rustproofing property suitable for galvanized steel sheet has been reached. Hereinafter, the paint will be described in detail.
一般にカチオン電着塗料は、カチオン性のエポキシ樹脂とその樹脂の硬化剤を基本的成分としており、その他に顔料や添加剤を含み、水性媒体中に分散したものである。本発明のカチオン電着塗料は、前述のとおりその有用性が判明したケイ酸化合物を含有することを特徴としている。 Generally, a cationic electrodeposition coating material contains a cationic epoxy resin and a curing agent for the resin as basic components, and additionally contains a pigment and additives, and is dispersed in an aqueous medium. The cationic electrodeposition coating composition of the present invention is characterized by containing a silicate compound whose usefulness has been found as described above.
ここでケイ酸化合物とは、アルカリ性水溶液中でケイ酸イオンを溶出する化合物である。具体的には、ケイ酸化合物１質量％含有ｐＨ１２のアルカリ性水溶液中に溶出したケイ酸イオンの平衡濃度５０ppm〜３０００ppm、好ましくは１００ppm以上を有する化合物をいう。この溶出するケイ酸イオンの平衡濃度が５０ppm未満であると、十分な耐食効果が得られず、より低い場合はより顕著となる。 Here, the silicate compound is a compound that elutes silicate ions in an alkaline aqueous solution. Specifically, it refers to a compound having an equilibrium concentration of silicate ion of 50 ppm to 3000 ppm, preferably 100 ppm or more, eluted in an alkaline aqueous solution having a pH of 12 containing 1% by mass of a silicate compound. When the equilibrium concentration of the eluted silicate ions is less than 50 ppm, a sufficient corrosion resistance effect cannot be obtained, and when it is lower, the effect becomes more remarkable.
さらに、ケイ酸化合物は、ｐH１２以下のアルカリ性水溶液中ではケイ酸イオン溶出量は多くないが、ｐH１２以上においてケイ酸イオン溶出量が増大する化合物が好ましい。このような化合物を含有するカチオン電着塗料組成物は、強アルカリ条件下で腐食されやすい性質を有する、亜鉛めっき鋼板のカチオン電着塗装法に適しているからである。 Furthermore, the silicate compound does not have a large amount of silicate ion eluted in an alkaline aqueous solution having a pH of 12 or less, but a compound which increases the silicate ion elution amount at a pH of 12 or more is preferable. This is because a cationic electrodeposition coating composition containing such a compound has a property of being easily corroded under strong alkaline conditions and is suitable for the cationic electrodeposition coating method of a galvanized steel sheet.
ケイ酸を含む化合物には、一般的に塗料に配合される顔料に分類されるものもあるが、本発明のケイ酸化合物は上記範囲の溶出平衡濃度を有するものをいい、それ以外のものは顔料に分類される。即ち、上記範囲の溶出平衡濃度を有しない顔料は本発明でいうケイ酸化合物には含まれない。本発明で用いるケイ酸化合物の例としては、ケイ酸亜鉛、ケイ酸カルシウム、シリカなどが挙げられる。ここで一般にシリカは二酸化ケイ素を主成分とする固体状物質をいうが、ケイ酸を溶出する能力はシリカの形状等により異なり得ると考えられる。本発明においては、ケイ酸化合物として多孔質であるシリカ粒子を使用することが好ましい。シリカ粒子が多孔質であることによってその内部表面が大きくなり、その結果、シリカ粒子からケイ酸イオンが多く溶出すると考えられるためである。多孔質であるシリカ粒子として、いわゆる湿式法を用いてケイ酸ソーダと酸とを混合することにより得られる、富士シリシア化学株式会社から市販されているサイリシアが挙げられる。 Some compounds containing silicic acid are generally classified as pigments to be incorporated into paints, but the silicate compound of the present invention refers to those having an elution equilibrium concentration in the above range, and other compounds Classified as pigment. That is, pigments having no elution equilibrium concentration in the above range are not included in the silicate compound according to the present invention. Examples of the silicate compound used in the present invention include zinc silicate, calcium silicate, silica and the like. Here, silica generally refers to a solid substance containing silicon dioxide as a main component, but it is considered that the ability to elute silicic acid may vary depending on the shape of the silica and the like. In the present invention, it is preferable to use porous silica particles as the silicate compound. This is because the porous silica particles have a large inner surface, and as a result, a large amount of silicate ions are eluted from the silica particles. Examples of the porous silica particles include thyrica commercially available from Fuji Silysia Chemical Ltd., which is obtained by mixing sodium silicate and an acid using a so-called wet method.
ケイ酸化合物は、固体状物質で後述する顔料の一部を構成するとも考えることができる。その場合、後述する顔料の一部が本発明のケイ酸化合物と置きかえられるものと考えることができる。従って、上記ケイ酸化合物の配合量は、顔料に対して１〜６０質量％であることが好ましく、さらには３〜４０質量％、特に５〜２５質量％であることが好ましい。６０質量％を超えて添加することは、分散ペーストの安定性が不良となる欠点を有することとなる。逆に、１質量％より少ない量の添加は、ケイ酸化合物の添加による効果(耐食効果)が不十分となる。本発明のケイ酸化合物を顔料の一部と考えないで、添加剤として捉えることも可能であり、その場合電着塗料中への配合量は、塗料の樹脂固形分１００質量部に対し、０．５〜２０質量部、好ましくは１〜１５質量部、より好ましくは３〜１０質量部である。添加量の多い場合と少ない場合の欠点は前述の顔料の一部と考える場合と同じである。但し、添加剤として考える場合は、顔料の添加量が必然的に少なくなる。 The silicate compound may be considered to be a solid substance and constitute a part of a pigment described below. In that case, it can be considered that some of the pigments described below can be replaced with the silicate compound of the present invention. Therefore, the compounding amount of the silicate compound is preferably 1 to 60% by mass, more preferably 3 to 40% by mass, and particularly preferably 5 to 25% by mass based on the pigment. Addition of more than 60% by mass has a disadvantage that the stability of the dispersed paste becomes poor. Conversely, if the amount is less than 1% by mass, the effect (corrosion resistance) of the addition of the silicate compound becomes insufficient. The silicate compound of the present invention can be considered as an additive without considering it as a part of the pigment. In this case, the compounding amount in the electrodeposition paint is 0% based on 100 parts by mass of the resin solid content of the paint. 0.5 to 20 parts by mass, preferably 1 to 15 parts by mass, more preferably 3 to 10 parts by mass. The disadvantages when the addition amount is large and when the addition amount is small are the same as those when the addition amount is considered as a part of the pigment. However, when considered as an additive, the amount of the pigment to be added is inevitably reduced.
所望により、ケイ酸化合物に加えて、アルミニウム化合物を併用することもできる。またケイ酸化合物に加えて、マグネシウム化合物を併用することもできる。さらに、ケイ酸化合物にアルミニウム化合物とマグネシウム化合物を加えて併用することもできる。アルミニウムイオン、マグネシウムイオンによる亜鉛めっき鋼板腐食減量抑制効果も高いからである(実験２参照)。また、ケイ酸イオンとアルミニウムイオンが同時にあるときに高い防錆作用が示される(実験３参照)。 If desired, an aluminum compound can be used in addition to the silicate compound. In addition to the silicate compound, a magnesium compound can be used in combination. Further, an aluminum compound and a magnesium compound may be added to the silicate compound and used together. This is because aluminum ions and magnesium ions also have a high effect of suppressing corrosion weight loss of galvanized steel sheet (see Experiment 2). Further, when silicate ions and aluminum ions are present at the same time, a high rust preventive action is exhibited (see Experiment 3).
本発明で使用するアルミニウム化合物は、アルカリ性水溶液中でアルミニウムイオンを溶出する化合物である。具体的には、本発明で使用するアルミニウム化合物は、アルミニウム化合物１質量％含有ｐＨ１２のアルカリ性水溶液中に溶出したアルミニウムイオンの平衡濃度５０ppm〜３０００ppm、好ましくは１００ppm以上を有する化合物をいう。アルミニウムを含有する化合物には、一般的に顔料に分類されるものもあるが、本発明のアルミニウム化合物は上記範囲の溶出平衡濃度を有するものをいい、上記の溶出濃度を有しない顔料は本発明でいうアルミニウム化合物には含まれない。 ア ル ミ ニ ウ ム The aluminum compound used in the present invention is a compound that elutes aluminum ions in an alkaline aqueous solution. Specifically, the aluminum compound used in the present invention refers to a compound having an equilibrium concentration of aluminum ions of 50 ppm to 3000 ppm, preferably 100 ppm or more, eluted in an alkaline aqueous solution containing 1% by mass of the aluminum compound and having a pH of 12. Some aluminum-containing compounds are generally classified as pigments, but the aluminum compound of the present invention refers to a compound having an elution equilibrium concentration in the above range. Are not included in the aluminum compound.
使用できるアルミニウム化合物として、例えばアルミナ、水酸化アルミニウム、アルミニウム粉末、リン酸アルミニウム、トリポリリン酸アルミニウム等が挙げられる。 ア ル ミ ニ ウ ム Aluminum compounds that can be used include, for example, alumina, aluminum hydroxide, aluminum powder, aluminum phosphate, and aluminum tripolyphosphate.
アルミニウム化合物をケイ酸化合物と併用する場合、上記配合量において、ケイ酸化合物の一部をアルミニウム化合物に置き換えて使用することとなる。ケイ酸化合物とアルミニウム化合物の配合比は、１００／１０〜１００／１０００、好ましくは１００／５０〜１００／１００の範囲である。ケイ酸化合物およびアルミニウム化合物の含有量は、電着塗料の樹脂固形分１００質量部に対して、０．５〜２０質量部、好ましくは１〜１５質量部、より好ましくは３〜１０質量部である。 (4) When an aluminum compound is used in combination with a silicate compound, a part of the silicate compound is replaced with an aluminum compound in the above-mentioned amount. The compounding ratio of the silicate compound and the aluminum compound is in the range of 100/10 to 100/1000, preferably 100/50 to 100/100. The content of the silicate compound and the aluminum compound is 0.5 to 20 parts by mass, preferably 1 to 15 parts by mass, more preferably 3 to 10 parts by mass, based on 100 parts by mass of the resin solid content of the electrodeposition coating composition. is there.
本発明で使用するマグネシウム化合物は、アルカリ性水溶液中でマグネシウムイオンを溶出する化合物である。具体的には、本発明で使用するマグネシウム化合物は、マグネシウム化合物１質量％含有ｐＨ１２のアルカリ性水溶液中に溶出したマグネシウムイオンの平衡濃度５０ppm〜３０００ppm、好ましくは１００ppm以上を有する化合物をいう。マグネシウムを含有する化合物には、一般的に顔料に分類されるものもあるが、本発明のマグネシウム化合物は上記範囲の溶出平衡濃度を有するものをいい、上記の溶出濃度を有しない顔料は本発明でいうマグネシウム化合物には含まれない。 マ グ ネ シ ウ ム The magnesium compound used in the present invention is a compound that elutes magnesium ions in an alkaline aqueous solution. Specifically, the magnesium compound used in the present invention refers to a compound having an equilibrium concentration of magnesium ion of 50 ppm to 3000 ppm, preferably 100 ppm or more, eluted in an alkaline aqueous solution containing 1% by mass of the magnesium compound and having a pH of 12. Some magnesium-containing compounds are generally classified as pigments, but the magnesium compound of the present invention refers to a compound having an elution equilibrium concentration in the above range, and a pigment not having the above-mentioned elution concentration is the present invention. It is not included in the magnesium compound.
使用できるマグネシウム化合物として、例えば水酸化マグネシウム、マグネシウム粉末、リン酸マグネシウム等が挙げられる。 マ グ ネ シ ウ ム Examples of usable magnesium compounds include magnesium hydroxide, magnesium powder, magnesium phosphate and the like.
マグネシウム化合物をケイ酸化合物と併用する場合、上記配合量において、ケイ酸化合物の一部をマグネシウム化合物に置き換えて使用することとなる。ケイ酸化合物とマグネシウム化合物の配合比は、１００／１０〜１００／１０００、好ましくは１００／５０〜１００／１００の範囲である。ケイ酸化合物およびマグネシウム化合物の含有量は、電着塗料の樹脂固形分１００質量部に対して、０．５〜２０質量部、好ましくは１〜１５質量 (4) When a magnesium compound is used in combination with a silicate compound, a part of the silicate compound is replaced with a magnesium compound in the above-mentioned amount. The compounding ratio of the silicic acid compound and the magnesium compound is in the range of 100/10 to 100/1000, preferably 100/50 to 100/100. The content of the silicic acid compound and the magnesium compound is 0.5 to 20 parts by mass, preferably 1 to 15 parts by mass based on 100 parts by mass of the resin solid content of the electrodeposition coating composition.
アルミニウム化合物およびマグネシウム化合物をケイ酸化合物と併用する場合、上記配合量において、ケイ酸化合物の一部をアルミニウム化合物およびマグネシウム化合物に置き換えて使用することとなる。ケイ酸化合物とアルミニウム化合物およびマグネシウム化合物との配合比は、１００／１０〜１００／１０００、好ましくは１００／５０〜１００／１００の範囲である。ケイ酸化合物、アルミニウム化合物およびマグネシウム化合物の含有量は、電着塗料の樹脂固形分１００質量部に対して、０．５〜２０質量部、好ましくは１〜１５質量部、より好ましくは３〜１０質量部である。 When the aluminum compound and the magnesium compound are used in combination with the silicate compound, a part of the silicate compound is replaced with the aluminum compound and the magnesium compound in the above-mentioned amount. The compounding ratio of the silicic acid compound to the aluminum compound and the magnesium compound is in the range of 100/10 to 100/1000, preferably 100/50 to 100/100. The content of the silicate compound, the aluminum compound and the magnesium compound is 0.5 to 20 parts by mass, preferably 1 to 15 parts by mass, more preferably 3 to 10 parts by mass, based on 100 parts by mass of the resin solid content of the electrodeposition paint. Parts by weight.
本発明の無鉛性カチオン電着塗料組成物は、ケイ酸化合物等（ケイ酸化合物および所望によりアルミニウム化合物および/またはマグネシウム化合物を含むものをいう）以外に、カチオン性のエポキシ樹脂、硬化剤および必要に応じて顔料や添加剤を含むものである。以下、それぞれの成分について説明する。 The lead-free cationic electrodeposition coating composition of the present invention comprises a cationic epoxy resin, a curing agent and a silicate compound in addition to a silicate compound (including a silicate compound and optionally an aluminum compound and / or a magnesium compound). Depending on the content of the pigment and additives. Hereinafter, each component will be described.
カチオン性エポキシ樹脂
本発明で用いるカチオン性エポキシ樹脂には、アミンで変性されたエポキシ樹脂が含まれる。このカチオン性エポキシ樹脂は、特開昭５４−４９７８号、同昭５６−３４１８６号などに記載されている公知の樹脂でよい。
Cationic epoxy resin The cationic epoxy resin used in the present invention includes an epoxy resin modified with an amine. The cationic epoxy resin may be a known resin described in JP-A-54-4978 and JP-A-56-34186.
カチオン性エポキシ樹脂は、典型的には、ビスフェノール型エポキシ樹脂のエポキシ環の全部をカチオン性基を導入し得る活性水素化合物で開環するか、または一部のエポキシ環を他の活性水素化合物で開環し、残りのエポキシ環をカチオン性基を導入し得る活性水素化合物で開環して製造される。 The cationic epoxy resin typically opens all of the epoxy rings of the bisphenol-type epoxy resin with an active hydrogen compound capable of introducing a cationic group, or partially opens the epoxy ring with another active hydrogen compound. It is produced by ring opening and ring opening of the remaining epoxy ring with an active hydrogen compound capable of introducing a cationic group.
ビスフェノール型エポキシ樹脂の典型例はビスフェノールＡ型またはビスフェノールＦ型エポキシ樹脂である。前者の市販品としてはエピコート８２８（油化シェルエポキシ社製、エポキシ当量１８０〜１９０）、エピコート１００１（同、エポキシ当量４５０〜５００）、エピコート１０１０（同、エポキシ当量３０００〜４０００）などがあり、後者の市販品としてはエピコート８０７、（同、エポキシ当量１７０）などがある。 典型 A typical example of the bisphenol type epoxy resin is a bisphenol A type or bisphenol F type epoxy resin. Examples of the former commercially available products include Epikote 828 (Epoxy equivalent: 180 to 190, manufactured by Yuka Shell Epoxy), Epikote 1001 (Epoxy equivalent: 450 to 500), Epikote 1010 (Epoxy equivalent: 3000 to 4000), and the like. The latter commercially available products include Epicoat 807 and (Epoxy equivalent 170).
特開平５−３０６３２７号公報第０００４段落の式、化３に記載のような、オキサゾリドン環含有エポキシ樹脂をカチオン性エポキシ樹脂として用いてもよい。耐熱性及び耐食性に優れた塗膜が得られるからである。 オ キ サ An oxazolidone ring-containing epoxy resin as described in the formula (3) of JP-A-5-306327, paragraph 0004 may be used as the cationic epoxy resin. This is because a coating film having excellent heat resistance and corrosion resistance can be obtained.
エポキシ樹脂にオキサゾリドン環を導入する方法としては、例えば、メタノールのような低級アルコールでブロックされたブロックポリイソシアネートとポリエポキシドを塩基性触媒の存在下で加熱保温し、副生する低級アルコールを系内より留去することで得られる。 As a method of introducing an oxazolidone ring into an epoxy resin, for example, a blocked polyisocyanate and a polyepoxide blocked with a lower alcohol such as methanol are heated and maintained in the presence of a basic catalyst, and the lower alcohol as a by-product is removed from the system. Obtained by distillation.
特に好ましいエポキシ樹脂はオキサゾリドン環含有エポキシ樹脂である。耐熱性及び耐食性に優れ、更に耐衝撃性にも優れた塗膜が得られるからである。 A particularly preferred epoxy resin is an oxazolidone ring-containing epoxy resin. This is because a coating film excellent in heat resistance and corrosion resistance and also excellent in impact resistance can be obtained.
二官能エポキシ樹脂とモノアルコールでブロックしたジイソシアネート（すなわち、ビスウレタン）とを反応させるとオキサゾリドン環を含有するエポキシ樹脂が得られることは公知である。このオキサゾリドン環含有エポキシ樹脂の具体例及び製造方法は、例えば、特開２０００−１２８９５９号公報第００１２〜００４７段落に記載されている。 It is known that an epoxy resin containing an oxazolidone ring can be obtained by reacting a bifunctional epoxy resin with a diisocyanate blocked with a monoalcohol (that is, bisurethane). Specific examples and production methods of this oxazolidone ring-containing epoxy resin are described, for example, in JP-A-2000-128959, paragraphs 0012 to 0047.
これらのエポキシ樹脂は、ポリエステルポリオール、ポリエーテルポリオール、および単官能性のアルキルフェノールのような適当な樹脂で変性しても良い。また、エポキシ樹脂はエポキシ基とジオール又はジカルボン酸との反応を利用して鎖延長することができる。 These epoxy resins may be modified with suitable resins such as polyester polyols, polyether polyols, and monofunctional alkylphenols. In addition, the epoxy resin can be chain-extended utilizing a reaction between an epoxy group and a diol or dicarboxylic acid.
これらのエポキシ樹脂は、開環後０．３〜４．０ｍｅｑ／ｇのアミン当量となるように、より好ましくはそのうちの５〜５０％が１級アミノ基が占めるように活性水素化合物で開環するのが望ましい。 These epoxy resins are ring-opened with an active hydrogen compound so as to have an amine equivalent of 0.3 to 4.0 meq / g after ring opening, more preferably 5 to 50% of them are occupied by primary amino groups. It is desirable to do.
カチオン性基を導入し得る活性水素化合物としては１級アミン、２級アミン、３級アミンの酸塩、スルフィド及び酸混合物がある。本発明の１級、２級又は／及び３級アミノ基含有エポキシ樹脂を調製するためには１級アミン、２級アミン、３級アミンの酸塩をカチオン性基を導入し得る活性水素化合物として用いる。 (4) Examples of the active hydrogen compound into which a cationic group can be introduced include primary amine, secondary amine, tertiary amine acid salt, sulfide and acid mixture. In order to prepare the primary, secondary and / or tertiary amino group-containing epoxy resin of the present invention, an acid salt of a primary amine, a secondary amine or a tertiary amine is used as an active hydrogen compound capable of introducing a cationic group. Used.
具体例としては、ブチルアミン、オクチルアミン、ジエチルアミン、ジブチルアミン、メチルブチルアミン、モノエタノールアミン、ジエタノールアミン、Ｎ−メチルエタノールアミン、トリエチルアミン塩酸塩、Ｎ，Ｎ−ジメチルエタノールアミン酢酸塩、ジエチルジスルフィド・酢酸混合物などのほか、アミノエチルエタノールアミンのケチミン、ジエチレントリアミンのジケチミンなどの１級アミンをブロックした２級アミンがある。アミン類は複数のものを併用して用いてもよい。 Specific examples include butylamine, octylamine, diethylamine, dibutylamine, methylbutylamine, monoethanolamine, diethanolamine, N-methylethanolamine, triethylamine hydrochloride, N, N-dimethylethanolamine acetate, and a mixture of diethyl disulfide and acetic acid. And secondary amines in which primary amines such as aminoethylethanolamine ketimine and diethylenetriamine diketimine are blocked. The amines may be used in combination of two or more.
硬化剤
本発明で使用する硬化剤は、ポリイソシアネートをブロック剤でブロックして得られたブロックポリイソシアネートが好ましく、ここでポリイソシアネートとは、１分子中にイソシアネート基を２個以上有する化合物をいう。ポリイソシアネートとしては、例えば、脂肪族系、脂環式系、芳香族系および芳香族−脂肪族系等のうちのいずれのものであってもよい。
Curing agent The curing agent used in the present invention is preferably a blocked polyisocyanate obtained by blocking a polyisocyanate with a blocking agent, where the polyisocyanate is a compound having two or more isocyanate groups in one molecule. . As the polyisocyanate, for example, any one of an aliphatic system, an alicyclic system, an aromatic system, and an aromatic-aliphatic system may be used.
ポリイソシアネートの具体例には、トリレンジイソシアネート（ＴＤＩ）、ジフェニルメタンジイソシアネート（ＭＤＩ）、ｐ−フェニレンジイソシアネート、及びナフタレンジイソシアネート等のような芳香族ジイソシアネート；ヘキサメチレンジイソシアネート（ＨＤＩ）、２，２，４−トリメチルヘキサンジイソシアネート、及びリジンジイソシアネート等のような炭素数３〜１２の脂肪族ジイソシアネート；１，４−シクロヘキサンジイソシアネート（ＣＤＩ）、イソホロンジイソシアネート（ＩＰＤＩ）、４，４´−ジシクロヘキシルメタンジイソシアネート（水添ＭＤＩ）、メチルシクロヘキサンジイソシアネート、イソプロピリデンジシクロヘキシル−４，４´−ジイソシアネート、及び１，３−ジイソシアナトメチルシクロヘキサン（水添ＸＤＩ）、水添ＴＤＩ、２，５−もしくは２，６−ビス（イソシアナートメチル）−ビシクロ［２．２．１］ヘプタン（ノルボルナンジイソシアネートとも称される。）等のような炭素数５〜１８の脂環式ジイソシアネート；キシリレンジイソシアネート（ＸＤＩ）、及びテトラメチルキシリレンジイソシアネート（ＴＭＸＤＩ）等のような芳香環を有する脂肪族ジイソシアネート；これらのジイソシアネートの変性物（ウレタン化物、カーボジイミド、ウレトジオン、ウレトイミン、ビューレット及び／又はイソシアヌレート変性物）；等があげられる。これらは、単独で、または２種以上併用することができる。 Specific examples of the polyisocyanate include aromatic diisocyanates such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), p-phenylene diisocyanate, and naphthalene diisocyanate; hexamethylene diisocyanate (HDI); C3-C12 aliphatic diisocyanates such as trimethylhexane diisocyanate and lysine diisocyanate; 1,4-cyclohexane diisocyanate (CDI), isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI) , Methylcyclohexane diisocyanate, isopropylidene dicyclohexyl-4,4'-diisocyanate, and 1,3-diisocyanatomethylcyclo Carbon such as hexane (hydrogenated XDI), hydrogenated TDI, 2,5- or 2,6-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane (also referred to as norbornane diisocyanate) and the like. Aliphatic diisocyanates of several 5 to 18; aliphatic diisocyanates having an aromatic ring such as xylylene diisocyanate (XDI) and tetramethyl xylylene diisocyanate (TMXDI); modified products of these diisocyanates (urethane compounds, carbodiimides, Uretdione, uretoimine, buret and / or isocyanurate). These can be used alone or in combination of two or more.
ポリイソシアネートをエチレングリコール、プロピレングリコール、トリメチロールプロパン、ヘキサントリオールなどの多価アルコールとＮＣＯ／ＯＨ比２以上で反応させて得られる付加体ないしプレポリマーも硬化剤として使用してよい。 付 加 An adduct or prepolymer obtained by reacting a polyisocyanate with a polyhydric alcohol such as ethylene glycol, propylene glycol, trimethylolpropane or hexanetriol at an NCO / OH ratio of 2 or more may also be used as a curing agent.
ポリイソシアネートは、脂肪族ポリイソシアネート又は脂環式ポリイソシアネートであることが好ましい。形成される塗膜が耐候性に優れるからである。 The polyisocyanate is preferably an aliphatic polyisocyanate or an alicyclic polyisocyanate. This is because the formed coating film has excellent weather resistance.
脂肪族ポリイソシアネート又は脂環式ポリイソシアネートの好ましい具体例には、ヘキサメチレンジイソシアネート、水添ＴＤＩ、水添ＭＤＩ、水添ＸＤＩ、ＩＰＤＩ、ノルボルナンジイソシアネート、それらの二量体（ビウレット）、三量体（イソシアヌレート）等が挙げられる。 Preferred specific examples of the aliphatic polyisocyanate or the alicyclic polyisocyanate include hexamethylene diisocyanate, hydrogenated TDI, hydrogenated MDI, hydrogenated XDI, IPDI, norbornane diisocyanate, dimer (biuret), and trimer thereof. (Isocyanurate) and the like.
ブロック剤は、ポリイソシアネート基に付加し、常温では安定であるが解離温度以上に加熱すると遊離のイソシアネート基を再生し得るものである。 The blocking agent is one that is added to the polyisocyanate group and is stable at room temperature, but can regenerate a free isocyanate group when heated above the dissociation temperature.
ブロック剤としては、低温硬化（１６０℃以下）を望む場合には、ε−カプロラクタム、δ−バレロラクタム、γ−ブチロラクタムおよびβ−プロピオラクタムなどのラクタム系ブロック剤、及びホルムアルドキシム、アセトアルドキシム、アセトキシム、メチルエチルケトオキシム、ジアセチルモノオキシム、シクロヘキサンオキシムなどのオキシム系ブロック剤を使用するのが良い。 When low temperature curing (160 ° C. or lower) is desired, lactam blocking agents such as ε-caprolactam, δ-valerolactam, γ-butyrolactam and β-propiolactam, and formaldoxime, acetoald Oxime-based blocking agents such as oxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, and cyclohexane oxime are preferably used.
カチオン性エポキシ樹脂と硬化剤とを含むバインダーは、一般に、電着塗料組成物の全固形分の２５〜８５質量％、好ましくは４０〜７０質量％を占める量で電着塗料組成物に含有される。 The binder containing the cationic epoxy resin and the curing agent is generally contained in the electrodeposition coating composition in an amount occupying 25 to 85% by mass, preferably 40 to 70% by mass of the total solids of the electrodeposition coating composition. You.
顔料
電着塗料組成物には着色剤として一般に顔料を含有させる。本発明の電着塗料組成物にも通常用いられる顔料を配合してもよい。本明細書でいう「顔料」とは、前述のケイ酸化合物、アルミニウム化合物およびマグネシウム化合物を除いたものをいう。例えば、クレーやタルクなどはアルミニウムやケイ酸を含むが、これらは溶出平衡濃度が所定範囲を満足しないので、顔料として扱う。使用し得る顔料の例としては、チタンホワイト、カーボンブラック及びベンガラのような着色顔料；カオリン、タルク、ケイ酸アルミニウム、炭酸カルシウム、マイカおよびクレーのような体質顔料；リン酸亜鉛、リン酸鉄、リン酸カルシウム、亜リン酸亜鉛、シアン化亜鉛、酸化亜鉛、モリブデン酸亜鉛、モリブデン酸アルミニウム、モリブデン酸カルシウム及びリンモリブデン酸アルミニウム、リンモリブデン酸アルミニウム亜鉛のような防錆顔料等が挙げられる。
The pigment electrodeposition coating composition generally contains a pigment as a colorant. The electrodeposition coating composition of the present invention may also contain a commonly used pigment. As used herein, the term "pigment" refers to a pigment excluding the aforementioned silicate compound, aluminum compound and magnesium compound. For example, clay and talc contain aluminum and silicic acid, but these are treated as pigments because their elution equilibrium concentrations do not satisfy a predetermined range. Examples of pigments that can be used include coloring pigments such as titanium white, carbon black and red iron oxide; extender pigments such as kaolin, talc, aluminum silicate, calcium carbonate, mica and clay; zinc phosphate, iron phosphate, Examples include rust preventive pigments such as calcium phosphate, zinc phosphite, zinc cyanide, zinc oxide, zinc molybdate, aluminum molybdate, calcium molybdate and aluminum phosphomolybdate, and zinc aluminum phosphomolybdate.
顔料は、一般に、電着塗料組成物の全固形分の１〜３５質量％、好ましくは１０〜３０質量％を占める量で電着塗料組成物に含有される。前述のように、本発明に用いるケイ酸化合物等は、固体成分で顔料の一部と考えることもできるので、その場合は上記顔料の配合量の一部分をケイ酸化合物等にする。ケイ酸化合物等を添加剤として捉える場合には、顔料の配合量は少なくなり、塗料固形分の０.０１〜１５質量％、好ましくは０.２〜２質量％となる。 The pigment is generally contained in the electrodeposition coating composition in an amount of 1 to 35% by mass, preferably 10 to 30% by mass of the total solids of the electrodeposition coating composition. As described above, the silicate compound and the like used in the present invention can be considered as a solid component and a part of the pigment. In that case, a part of the blending amount of the pigment is changed to the silicate compound and the like. When a silicate compound or the like is considered as an additive, the amount of the pigment is reduced, and the amount is 0.01 to 15% by mass, preferably 0.2 to 2% by mass based on the solid content of the paint.
但し、本発明の電着塗料を無鉛性カチオン電着塗料とする場合は、鉛を含む耐食性付与剤、例えば、塩基性ケイ酸鉛、塩基性硫酸鉛、鉛丹、及びシアナミド鉛のような鉛系防錆顔料は使用しないか、または使用しても希釈塗料（電着浴へ加えられる状態）の鉛イオン濃度が１００ｐｐｍ以下となるような量で使用すべきである。鉛イオン濃度が高いと環境に有害であるからである。 However, when the electrodeposition paint of the present invention is a lead-free cationic electrodeposition paint, a corrosion-resistance imparting agent containing lead, for example, lead such as basic lead silicate, basic lead sulfate, lead tin, and cyanamide lead. The anticorrosive pigment should not be used, or should be used in such an amount that the concentration of lead ions in the diluted paint (when added to the electrodeposition bath) is 100 ppm or less even when used. This is because a high lead ion concentration is harmful to the environment.
顔料分散ペースト
顔料を電着塗料の成分として用いる場合、一般に顔料を顔料分散樹脂と呼ばれる樹脂と共に予め高濃度で水性媒体に分散させてペースト状にする。顔料は粉体状であるため、電着塗料組成物で用いる低濃度均一状態に一工程で分散させるのは困難だからである。一般にこのようなペーストを顔料分散ペーストという。
When a pigment dispersion paste pigment is used as a component of an electrodeposition coating material, the pigment is generally dispersed in an aqueous medium at a high concentration in advance together with a resin called a pigment dispersion resin to form a paste. This is because, since the pigment is in a powder form, it is difficult to disperse the pigment in a low concentration uniform state used in the electrodeposition coating composition in one step. Generally, such a paste is called a pigment dispersion paste.
顔料分散ペーストは、顔料を顔料分散樹脂ワニスと共に水性媒体中に分散させて調製する。本発明では、顔料と共にケイ酸化合物等も分散ペースト化するのが好ましい。顔料分散樹脂ワニスとしては、一般に、カチオン性又はノニオン性の低分子量界面活性剤や４級アンモニウム基及び／又は３級スルホニウム基を有する変性エポキシ樹脂等のようなカチオン性重合体を用いる。水性媒体としてはイオン交換水や少量のアルコール類を含む水等を用いる。一般に、顔料分散樹脂ワニスは５〜４０質量部、顔料は１０〜３０質量部の固形分比で用いる。 The pigment dispersion paste is prepared by dispersing a pigment in an aqueous medium together with a pigment dispersion resin varnish. In the present invention, it is preferable that a silicate compound and the like are also dispersed into a paste together with the pigment. As the pigment-dispersed resin varnish, a cationic or nonionic low molecular weight surfactant or a cationic polymer such as a modified epoxy resin having a quaternary ammonium group and / or a tertiary sulfonium group is generally used. As the aqueous medium, ion exchange water, water containing a small amount of alcohols, or the like is used. Generally, the pigment-dispersed resin varnish is used at a solid content ratio of 5 to 40 parts by mass, and the pigment is used at a solid content ratio of 10 to 30 parts by mass.
上記顔料分散用樹脂ワニスおよび顔料を、樹脂固形分１００質量部に対し１０〜１０００質量部混合した後、その混合物中の顔料の粒径が所定の均一な粒径となるまで、ボールミルやサンドグラインドミル等の通常の分散装置を用いて分散させて、顔料分散ペーストを得る。 After mixing the pigment dispersion resin varnish and the pigment in an amount of 10 to 1000 parts by mass with respect to 100 parts by mass of the resin solid content, a ball mill or a sand grinder is used until the particle size of the pigment in the mixture becomes a predetermined uniform particle size. The pigment is dispersed using an ordinary dispersing device such as a mill to obtain a pigment dispersion paste.
電着塗料組成物
本発明の電着塗料組成物は、カチオン性エポキシ樹脂、硬化剤、及びシリカ粒子を含む顔料分散ペーストを水性媒体中に分散することによって調製される。また、通常、水性媒体にはカチオン性エポキシ樹脂の分散性を向上させるために中和剤を含有させる。中和剤は塩酸、硝酸、リン酸、ギ酸、酢酸、乳酸のような無機酸または有機酸である。その量は少なくとも２０％、好ましくは３０〜６０％の中和率を達成する量である。
Electrodeposition coating composition The electrodeposition coating composition of the present invention is prepared by dispersing a pigment dispersion paste containing a cationic epoxy resin, a curing agent, and silica particles in an aqueous medium. Usually, a neutralizing agent is contained in the aqueous medium in order to improve the dispersibility of the cationic epoxy resin. Neutralizing agents are inorganic or organic acids such as hydrochloric, nitric, phosphoric, formic, acetic, lactic acids. The amount is that which achieves a neutralization of at least 20%, preferably 30-60%.
硬化剤の量は、硬化時にカチオン性エポキシ樹脂中の１級、２級又は／及び３級アミノ基、水酸基等の活性水素含有官能基と反応して良好な硬化塗膜を与えるのに十分でなければならず、一般にカチオン性エポキシ樹脂の硬化剤に対する固形分質量比で表して一般に９０／１０〜５０／５０、好ましくは８０／２０〜６５／３５の範囲である。 The amount of the curing agent is sufficient to react with active hydrogen-containing functional groups such as primary, secondary and / or tertiary amino groups and hydroxyl groups in the cationic epoxy resin during curing to give a good cured coating film. It should generally be in the range of 90/10 to 50/50, preferably 80/20 to 65/35, expressed as a mass ratio of solid content of the cationic epoxy resin to the curing agent.
電着塗料は、ジラウリン酸ジブチルスズ、ジブチルスズオキサイドのようなスズ化合物や、通常のウレタン開裂触媒を含むことができる。鉛を実質的に含まないものが好ましいため、その量はブロックポリイソシアネート化合物の０．１〜５質量％とすることが好ましい。 The electrodeposition paint can contain a tin compound such as dibutyltin dilaurate or dibutyltin oxide, or a usual urethane cleavage catalyst. Since it is preferable that the composition does not substantially contain lead, the amount is preferably 0.1 to 5% by mass of the blocked polyisocyanate compound.
電着塗料は、水混和性有機溶剤、界面活性剤、酸化防止剤、紫外線吸収剤、及び顔料などの常用の塗料用添加剤を含むことができる。 The electrodeposition paint may contain conventional paint additives such as a water-miscible organic solvent, a surfactant, an antioxidant, an ultraviolet absorber, and a pigment.
本発明の電着塗料組成物は当業者に周知の方法で被塗物に電着塗装され、硬化塗膜を形成する。このカチオン電着塗料組成物を用いて電着塗装を行う場合の被塗物は、予め、浸漬、スプレー方法等によりリン酸亜鉛処理等の表面処理の施された導体であることが好ましいが、この表面処理が施されていないものであっても良い。また、導体とは、電着塗装を行うに当り、陰極になり得るものであれば特に制限はなく、金属基材が好ましい。 電 The electrodeposition coating composition of the present invention is electrodeposited on an object to be coated by a method well known to those skilled in the art to form a cured coating film. The object to be coated when performing the electrodeposition coating using the cationic electrodeposition coating composition is preferably a conductor that has been subjected to a surface treatment such as zinc phosphate treatment by dipping, spraying, or the like, It may not be subjected to this surface treatment. The conductor is not particularly limited as long as it can be a cathode in performing electrodeposition coating, and a metal substrate is preferable.
電着が実施される条件は一般的に他の型の電着塗装に用いられるものと同様である。印加電圧は大きく変化してもよく、１ボルト〜数百ボルトの範囲であってよい。電流密度は通常約１０アンペア/m2〜１６０アンペア/m2であり、電着中に減少する傾向にある。 The conditions under which electrodeposition is performed are generally the same as those used for other types of electrodeposition coating. The applied voltage can vary greatly and can range from one volt to several hundred volts. Current densities are typically about 10 amps / m 2 to 160 amps / m 2 and tend to decrease during electrodeposition.
電着後、被膜を昇温下に通常の方法、例えば焼付炉中、焼成オーブン中あるいは赤外ヒートランプで焼付ける。焼付け温度は変化してもよいが、通常約１４０℃〜１８０℃である。 After the electrodeposition, the coating is baked at an elevated temperature in a usual manner, for example, in a baking furnace, in a baking oven or with an infrared heat lamp. The baking temperature may vary, but is usually between about 140C and 180C.
以下の実験、製造例および実施例は、限定でなく例示目的のみで与えられる。これらにおいて「部」および「％」は特記しない限り質量基準による。「エポキシ当量」「アミン当量」は固形分当りの数値を示す。 実 験 The following experiments, preparations and examples are given by way of illustration only and not by way of limitation. In these, “parts” and “%” are based on mass unless otherwise specified. “Epoxy equivalent” and “amine equivalent” indicate numerical values per solid content.
実験１（鋼板別の腐食）
表面積２２.５cm2の、亜鉛めっき鋼板、冷間圧延鋼板(ＳＰＣ)および亜鉛−ニッケルめっき鋼板(Ｚｎ−Ｎｉ)の試験片を作成し、それらの質量を測定した。５％ＮａＣｌ水溶液をそれぞれｐＨ３〜１３に調整した。これらのｐＨ調整５％ＮａＣｌ水溶液に、上記試験片を５０℃、５日間浸漬した。その後、試験片を取り出して乾燥し、浸漬後の質量を測定して浸漬前の質量と比較し、減少分を腐食減量とした。結果を図１に示す。
Experiment 1 (corrosion by steel sheet)
Test specimens of a galvanized steel sheet, a cold-rolled steel sheet (SPC) and a zinc-nickel plated steel sheet (Zn-Ni) having a surface area of 22.5 cm 2 were prepared, and their masses were measured. 5% NaCl aqueous solution was adjusted to pH 3 to 13, respectively. The test piece was immersed in a 5% aqueous NaCl solution at 50 ° C. for 5 days. Thereafter, the test piece was taken out and dried, the mass after immersion was measured and compared with the mass before immersion, and the decrease was regarded as the corrosion weight loss. The results are shown in FIG.
図１より、冷間圧延鋼板、亜鉛−ニッケルめっき鋼板に比べて、亜鉛めっき鋼板はアルカリ性条件下で腐食が大きいことが解る。 よ り From FIG. 1, it can be seen that the galvanized steel sheet corrodes more under alkaline conditions than the cold-rolled steel sheet and the zinc-nickel plated steel sheet.
実験２（アルカリ域での各イオン種の効果）
表面積２２.５cm2の、亜鉛めっき鋼板の試験片を、ケイ酸、モリブデン酸、リン酸、マグネシウム、アルミニウムおよび亜鉛からなるイオン種のうち１種を含有する５％ＮａＣｌ水溶液(ｐＨ１１に調整)に、５０℃、５日間浸漬した。その後、試験片を取り出して乾燥し、浸漬後の質量を測定して浸漬前の質量と比較し、減少分を腐食減量とした。結果を図２に示す。
Experiment 2 (Effect of each ion species in alkaline area)
A test piece of galvanized steel sheet having a surface area of 22.5 cm 2 was placed in a 5% aqueous NaCl solution (adjusted to pH 11) containing one of ionic species consisting of silicic acid, molybdic acid, phosphoric acid, magnesium, aluminum and zinc. At 50 ° C. for 5 days. Thereafter, the test piece was taken out and dried, the mass after immersion was measured and compared with the mass before immersion, and the decrease was regarded as the corrosion weight loss. FIG. 2 shows the results.
図２より、ケイ酸イオンによる腐食減量抑制効果が、特に低濃度下で極めて高いことが解る。さらにアルミニウムイオン、マグネシウムイオンによる腐食減量抑制効果も高いことが解る。 よ り From FIG. 2, it can be seen that the effect of suppressing corrosion weight loss by silicate ions is extremely high, especially at low concentrations. Furthermore, it is understood that the effect of suppressing corrosion weight loss by aluminum ions and magnesium ions is high.
実験３（ケイ酸イオンおよびアルミニウムイオンの共存効果）
表面積２２.５cm2の、亜鉛めっき鋼板の試験片を、ケイ酸、アルミニウムのいずれか一方または両方を含有する５％ＮａＣｌ水溶液(ｐＨ１２、１２.６)に、５０℃、５日間浸漬した。その後、試験片を取り出して乾燥し、浸漬後の質量を測定して浸漬前の質量と比較し、減少分を腐食減量とした。結果を図３、図４に示す。
Experiment 3 (Coexistence effect of silicate ion and aluminum ion)
A test piece of galvanized steel sheet having a surface area of 22.5 cm 2 was immersed in a 5% aqueous NaCl solution (
図３、図４より、ケイ酸イオンとアルミニウムイオンが共存するときに、腐食減量抑制効果が高いことが解る。 、 From FIGS. 3 and 4, it can be seen that when silicate ions and aluminum ions coexist, the effect of suppressing corrosion weight loss is high.
製造例１（カチオン性エポキシ樹脂の製造）
攪拌機、冷却管、窒素導入管、温度計および滴下漏斗を装備したフラスコに、２，４−／２，６−トリレンジイソシアネート（質量比＝８／２）９２部、メチルイソブチルケトン（以下、ＭＩＢＫという）９５部およびジブチルスズジラウレート０．５部を仕込んだ。その混合物を攪拌しながら、メタノール２１部を添加した。その反応は、室温から始め、発熱により６０℃まで昇温し、その後３０分間反応を継続した後、エチレングリコールモノ−２−エチルヘキシルエーテル５７部を滴下漏斗により滴下した。更にビスフェノールＡ−プロピレンオキシド５モル付加体（商品名ニューポールＢＰ−５Ｐ、三洋化成社製）４２部を添加した。反応は主に６０〜６５℃の範囲で行い、ＩＲスペクトルの測定において、イソシアネート基に基づく吸収が消失するまで継続した。
Production Example 1 (Production of cationic epoxy resin)
In a flask equipped with a stirrer, a condenser, a nitrogen inlet, a thermometer and a dropping funnel, 92 parts of 2,4- / 2,6-tolylene diisocyanate (mass ratio = 8/2), methyl isobutyl ketone (hereinafter, MIBK) 95 parts) and 0.5 part of dibutyltin dilaurate. While stirring the mixture, 21 parts of methanol was added. The reaction was started at room temperature, heated to 60 ° C. due to heat generation, and continued for 30 minutes, after which 57 parts of ethylene glycol mono-2-ethylhexyl ether was added dropwise using a dropping funnel. Further, 42 parts of a 5-mol bisphenol A-propylene oxide adduct (trade name: Newpol BP-5P, manufactured by Sanyo Chemical Co., Ltd.) was added. The reaction was performed mainly in the range of 60 to 65 ° C., and was continued until the absorption based on the isocyanate group disappeared in the measurement of the IR spectrum.
次に、エポキシ当量１８８のビスフェノールＡ型エポキシ樹脂（商品名ＤＥＲ−３３１Ｊ、ダウケミカル社製）３６５部を、上記の反応混合物に加えて１２５℃まで昇温した。その後、ベンジルジメチルアミン１．０部を添加し、エポキシ当量４１０になるまで１３０℃で反応させた。 Next, 365 parts of a bisphenol A type epoxy resin having an epoxy equivalent of 188 (trade name: DER-331J, manufactured by Dow Chemical Company) was added to the above reaction mixture, and the temperature was raised to 125 ° C. Thereafter, 1.0 part of benzyldimethylamine was added and reacted at 130 ° C. until the epoxy equivalent reached 410.
続いて、ビスフェノールＡ８７部を加えて１２０℃で反応させ、エポキシ当量１１９０とした。その後、上記反応混合物を冷却し、ジエタノールアミン１１部、Ｎ−エチルエタノールアミン２４部およびアミノエチルエタノールアミンのケチミン化物の７９％ＭＩＢＫ溶液２５部を加え、１１０℃で２時間反応させた。その後、ＭＩＢＫで不揮発分８０％となるまで希釈し、カチオン性エポキシ樹脂（樹脂固形分８０％）を得た。 Subsequently, 87 parts of bisphenol A was added and reacted at 120 ° C. to obtain an epoxy equivalent of 1190. Thereafter, the reaction mixture was cooled, 11 parts of diethanolamine, 24 parts of N-ethylethanolamine and 25 parts of a 79% MIBK solution of a ketimine compound of aminoethylethanolamine were added, and the mixture was reacted at 110 ° C. for 2 hours. Thereafter, the mixture was diluted with MIBK until the nonvolatile content became 80% to obtain a cationic epoxy resin (resin solid content 80%).
製造例２（ブロックポリイソシアネート硬化剤の合成）
製造例１と同様のフラスコに、２，５−および２，６−ビス（イソシアナトメチル）−ビシクロ［２．２．１］ヘプタン（三井東圧社製、イソシアネート当量１０３）７２３部、ＭＩＢＫ３３３部およびジブチルスズジラウレート０．０１部を仕込んだ。得られた反応混合物を７０℃まで昇温し、その反応混合物が均一に溶解した後、メチルエチルケトオキシム６１０部を２時間かけて滴下した。滴下終了後、反応温度を７０℃に保持したまま、ＩＲスペクトルの測定において、イソシアネート基に基づく吸収が消失するまで反応を継続させて、メチルエチルケトオキシムブロックポリイソシアネート硬化剤を得た。（樹脂固形分８０％）
Production Example 2 (Synthesis of blocked polyisocyanate curing agent)
In a flask similar to that of Production Example 1, 723 parts of 2,5- and 2,6-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane (manufactured by Mitsui Toatsu Co., isocyanate equivalent 103), 723 parts of MIBK And 0.01 part of dibutyltin dilaurate. The obtained reaction mixture was heated to 70 ° C., and after the reaction mixture was uniformly dissolved, 610 parts of methyl ethyl ketoxime was added dropwise over 2 hours. After the completion of the dropwise addition, the reaction was continued while maintaining the reaction temperature at 70 ° C. until the absorption based on the isocyanate group disappeared in the measurement of the IR spectrum to obtain a methyl ethyl ketoxime-blocked polyisocyanate curing agent. (Resin solid content 80%)
製造例３（スルホニウム基を有する顔料分散樹脂ワニスの製造）
攪拌装置、冷却管、窒素導入管および温度計を装備した反応容器に、イソホロンジイソシアネート（以下、ＩＰＤＩという）２２２．０部を入れ、ＭＩＢＫ３９．１部で希釈した後、ジブチルスズジラウレート０．２部を加えた。その後、５０℃に昇温した後、２−エチルヘキサノール１３１．５部を攪拌しながら、乾燥窒素雰囲気中で２時間かけて滴下した。適宜、冷却することにより、反応温度を５０℃に維持した。その結果、２−エチルヘキサノールハーフブロック化ＩＰＤＩが得られた。
適当な反応容器に、エポキシ当量１８８のビスフェノールＡ型エポキシ樹脂（ダウ・ケミカル・カンパニー社製）３８２．２部とビスフェノールＡ１１７．８部を仕込み、窒素雰囲気下、１５０〜１６０℃に加熱した。その反応混合物を１５０〜１６０℃で約１時間反応させ、次いで１２０℃に冷却した後、上記で調整された２−エチルヘキサノールハーフブロック化ＩＰＤＩ（ＭＩＢＫ溶液）２０９．８部を加えた。１４０〜１５０℃で１時間反応させた後、ポリアルキレンオキサイド化合物２０５部を加え、６０〜６５℃に冷却した。そこへ、１−（２−ヒドロキシエチルチオ）−２−プロパノール４０８．０部、脱イオン水１４４．０部、ジメチロールプロピオン酸１３４部を加え、酸価が１となるまで６５〜７５℃で反応させ、エポキシ樹脂に３級スルホニウム基を導入し、脱イオン水１５９５．２部を加えて３級化を終了させることにより、３級スルホニウム基を含有する顔料分散樹脂ワニスを得た（固形分３０％）。
Production Example 3 (Production of pigment dispersed resin varnish having sulfonium group)
222.0 parts of isophorone diisocyanate (hereinafter referred to as IPDI) was placed in a reaction vessel equipped with a stirrer, a cooling pipe, a nitrogen introduction pipe, and a thermometer, diluted with 39.1 parts of MIBK, and then 0.2 parts of dibutyltin dilaurate was added. added. Thereafter, after the temperature was raised to 50 ° C., 131.5 parts of 2-ethylhexanol was added dropwise over 2 hours in a dry nitrogen atmosphere while stirring. The reaction temperature was maintained at 50 ° C. by cooling appropriately. As a result, 2-ethylhexanol half-blocked IPDI was obtained.
In a suitable reaction vessel, 382.2 parts of a bisphenol A type epoxy resin having an epoxy equivalent of 188 (manufactured by Dow Chemical Company) and 117.8 parts of bisphenol A were charged and heated to 150 to 160 ° C. under a nitrogen atmosphere. The reaction mixture was reacted at 150 to 160 ° C. for about 1 hour, then cooled to 120 ° C., and 209.8 parts of the above-prepared 2-ethylhexanol half-blocked IPDI (MIBK solution) was added. After reacting at 140 to 150 ° C. for 1 hour, 205 parts of a polyalkylene oxide compound was added, and the mixture was cooled to 60 to 65 ° C. There, 408.0 parts of 1- (2-hydroxyethylthio) -2-propanol, 144.0 parts of deionized water and 134 parts of dimethylolpropionic acid are added, and the mixture is heated at 65 to 75 ° C. until the acid value becomes 1. After the reaction, a tertiary sulfonium group was introduced into the epoxy resin, 1595.2 parts of deionized water was added to terminate the tertiary conversion, and a pigment-dispersed resin varnish containing a tertiary sulfonium group was obtained (solid content). 30%).
製造例４（顔料分散ペーストの製造）
サンドグラインドミルに、製造例３で得られた顔料分散樹脂ワニスを固形分で６０部、カーボンブラック２．０部、表１に記載の顔料を１００．０部、二酸化チタン８０．０部、リンモリブデン酸アルミニウム１８．０部及びイオン交換水２２１．７部を入れ、粒度１０μｍ以下になるまで分散して、顔料分散ペーストを得た。
＊2シリカ粒子：富士シリシア化学株式会社製 サイリシア５３０。
＊3アルミニウム化合物：帝国化工株式会社製、Ｋ−ホワイト♯８４Ｓ（リン酸アルミニウム）。
＊4比較シリカ粒子：ＵＳ Ｓｉｌｉｃａ 社製、ミニシルＮｏ．５。
Production Example 4 (Production of pigment dispersion paste)
In a sand grind mill, 60 parts of the pigment-dispersed resin varnish obtained in Production Example 3 as solids, 2.0 parts of carbon black, 100.0 parts of the pigment described in Table 1, 80.0 parts of titanium dioxide, phosphorus 18.0 parts of aluminum molybdate and 221.7 parts of ion-exchanged water were added and dispersed until the particle size became 10 μm or less to obtain a pigment-dispersed paste.
* 2 Silica particles: Sylysia 530 manufactured by Fuji Silysia Chemical Ltd.
* 3 Aluminum compound: K-White # 84S (aluminum phosphate) manufactured by Teikoku Chemical Industries, Ltd.
* 4 Comparative silica particles: manufactured by US Silica, Minisil No. 5.
表１で用いた焼成カオリン、ケイ酸化合物(シリカ粒子)、アルミニウム化合物および比較シリカ粒子の１質量％をそれぞれｐH１２のアルカリ水溶液中に添加し、５０℃、３日後の溶出したケイ酸イオンおよびアルミニウムイオンの平衡濃度を測定した。結果を表２に示す。アルカリ水溶液は、水酸化ナトリウムをイオン交換水に添加し、ｐＨ１２に調整することにより作成した。
実施例１
製造例１のカチオン性エポキシ樹脂と製造例２のブロックポリイソシアネート硬化剤を固形分配合比７５：２５で均一に混合した後、エチレングリコールモノ−２−エチルヘキシルエーテルを固形分に対して３％になるように添加した。これに氷酢酸を加えて中和率４３．０％となるように中和し、更にイオン交換水を加えてゆっくり希釈した。固形分が３６．０％となるように減圧化でＭＩＢＫを除去することにより、メインエマルションを得た．このメインエマルション１５００．０部および製造例４(表１の配合１)により得た顔料分散ペースト５４１．７部をイオン交換水１９４９．３部及びジブチルスズオキサイド９．０部と混合して、固形分２０．０％のカチオン電着塗料を調整した。樹脂固形分１００質量部あたりのケイ酸化合物の含有量は６．６７質量部であった。
Example 1
After uniformly mixing the cationic epoxy resin of Production Example 1 and the blocked polyisocyanate curing agent of Production Example 2 at a solid content of 75:25, ethylene glycol mono-2-ethylhexyl ether was adjusted to 3% based on the solid content. It was added so that it became. Glacial acetic acid was added to the mixture to neutralize it to a neutralization rate of 43.0%, and the mixture was diluted slowly with ion-exchanged water. The MIBK was removed under reduced pressure so that the solid content was 36.0%, to obtain a main emulsion. 1500.0 parts of this main emulsion and 541.7 parts of the pigment dispersion paste obtained according to Production Example 4 (Formulation 1 in Table 1) were mixed with 1949.3 parts of ion-exchanged water and 9.0 parts of dibutyltin oxide to obtain a solid content. 20.0% of a cationic electrodeposition paint was prepared. The content of the silicate compound per 100 parts by mass of the resin solid content was 6.67 parts by mass.
実施例２
表１の配合１より得た顔料分散ペーストの代わりに配合２より得た顔料分散ペーストを用いた以外は、実施例１と同様にして、カチオン電着塗料を調製した。樹脂固形分１００質量部あたりのケイ酸化合物の含有量は１３．３質量部であった。
Example 2
A cationic electrodeposition paint was prepared in the same manner as in Example 1 except that the pigment dispersion paste obtained from
実施例３
表１の配合１より得た顔料分散ペーストの代わりに配合３より得た顔料分散ペーストを用いた以外は、実施例１と同様にして、カチオン電着塗料を調製した。樹脂固形分１００質量部あたりのケイ酸化合物およびアルミニウム化合物の含有量はそれぞれ６．６７質量部であった。
Example 3
A cationic electrodeposition paint was prepared in the same manner as in Example 1 except that the pigment dispersion paste obtained from Formulation 3 was used instead of the pigment dispersion paste obtained from Formulation 1 in Table 1. The content of each of the silicate compound and the aluminum compound per 100 parts by mass of the resin solid content was 6.67 parts by mass.
比較例１
表１の配合１より得た顔料分散ペーストの代わりに配合４より得た顔料分散ペーストを用いた以外は、実施例１と同様にして、カチオン電着塗料を調製した。
Comparative Example 1
A cationic electrodeposition paint was prepared in the same manner as in Example 1, except that the pigment dispersion paste obtained from
比較例２
表１の配合１より得た顔料ペーストの代わりに配合５より得た顔料ペーストを用いた以外は、実施例１と同様にして、カチオン電着塗料を調製した。
Comparative Example 2
A cationic electrodeposition paint was prepared in the same manner as in Example 1 except that the pigment paste obtained from
電着塗膜の評価
塩水浸耐食性
カチオン電着塗料組成物を、電気亜鉛めっき処理した鋼板に乾燥塗膜の膜厚が５μｍおよび７μｍになるように電着を行った。これを１６０℃で２５分焼き付けて得られたカチオン電着塗膜を、５％食塩水に５５℃で２２日間浸漬した後、ブリスタの面積の割合を以下の基準で評価した。結果を表３に示す。
Evaluation of Electrodeposited Film The salt water immersion corrosion-resistant cationic electrodeposition coating composition was electrodeposited on a steel plate which had been subjected to electrogalvanization so that the thickness of the dried coating film became 5 μm and 7 μm. This was baked at 160 ° C. for 25 minutes, and the resulting cationic electrodeposition coating film was immersed in a 5% saline solution at 55 ° C. for 22 days, and the area ratio of the blister was evaluated according to the following criteria. Table 3 shows the results.
◎： １０％以下
○： １０〜２０％
△： ２０〜３０％
×： ３０％以上
Δ: 20 to 30%
×: 30% or more
Claims (5)
The zinc plating according to any one of claims 1 to 4, wherein the silicate compound, the aluminum compound, or the magnesium compound is contained in the coating material in a total amount of 0.5 to 20 parts by mass per 100 parts by mass of the resin solid content. Cationic electrodeposition coating composition for steel sheet.
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